CN110790428A - Method for catalytic oxidation of emerging micropollutants by activated carbon-ceramic membrane-high-activity iron - Google Patents
Method for catalytic oxidation of emerging micropollutants by activated carbon-ceramic membrane-high-activity iron Download PDFInfo
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- CN110790428A CN110790428A CN201911132452.4A CN201911132452A CN110790428A CN 110790428 A CN110790428 A CN 110790428A CN 201911132452 A CN201911132452 A CN 201911132452A CN 110790428 A CN110790428 A CN 110790428A
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- activated carbon
- ferrate
- ceramic membrane
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
A method for catalyzing and oxidizing new micro-pollutants by activated carbon-ceramic membrane-high-activity iron. Ferrate has limited oxidizing ability and cannot oxidize organic pollutants with low electron cloud density; the surface of the activated carbon contains a large number of redox groups such as phenolic hydroxyl and benzoquinone, high-activity iron can be generated through electron transfer induction, and meanwhile, the activated carbon can activate hydrogen peroxide generated in situ to form active components such as hydroxyl radicals and the like, so that a high-activity iron and radical composite oxidation system is formed, and the removal of organic pollutants is enhanced. The ceramic membrane has the characteristic of oxidation corrosion resistance, and the active carbon can be effectively separated. In addition, oxidation of the active component can also alleviate the membrane fouling problem. The water treatment method of the invention comprises the following steps: adding a certain amount of high-iron and activated carbon into a water sample to be treated in a designed reaction tank, wherein redox groups on the surface of the activated carbon can react with the high-iron to generate high-activity pentavalent iron (Fe (V)) and tetravalent iron (Fe (IV)), and meanwhile, the activated carbon activates hydrogen peroxide or oxygen generated in situ to generate hydroxyl radicals, and the high-activity iron and the hydroxyl radicals can quickly oxidize pollutants which are not easily oxidized by ferrate; then, the separation of the activated carbon and the effluent is realized by utilizing the efficient separation function of the ceramic membrane, the quality of the effluent is ensured, and meanwhile, the problem of membrane pollution can be relieved by the oxidation of active components. The method is simple to operate, does not need additional water treatment equipment, and has good economic applicability and good application prospect.
Description
Technical Field
The invention relates to a water treatment method, in particular to a method for removing organic pollutants difficult to treat.
Background
With the rapid development of economy and the rapid increase of population in China, a large amount of various chemical organic pollutants, including personal care products, medicines, endocrine disruptors, pesticides and the like, are discharged into water, the influence on the water environment is increasingly prominent, and meanwhile, with the increasing improvement of environment detection technology, more and more organic chemical pollutants are detected in the water. Along with the deepening of people's understanding of organic chemical pollutants, the harm of organic chemical pollutants to water environment and the threat to human health are receiving more and more attention. This is mainly because these organic chemical pollutants are relatively harmful to the aqueous environment even at low concentrations, are difficult to degrade in natural environments, and are very easily concentrated in aqueous environments.
The conventional biological treatment process is difficult to remove organic pollutants, and the currently and generally adopted process is to add a chemical oxidation process or a membrane process in the conventional process treatment process to ensure the effluent quality. In recent years, a green oxidant, namely ferrate, attracts extensive attention of researchers, and compared with common oxidants such as ozone, liquid chlorine and the like, the product in the ferrate oxidation process is ferric oxyhydroxide with a coagulation aiding effect, so that toxic and harmful substances such as bromate, chlorinated byproducts and the like which cause secondary pollution are not generated. Ferrate, however, is a selective oxidant and is not capable of oxidizing organic pollutants with a low electron cloud density. Recently, studies show that the carbon nano tube can catalyze ferrate to generate high-activity intermediate state iron to enhance the degradation of organic pollutants, but the separation of the carbon nano tube from water after treatment is a great problem. The membrane separation technology has the advantages of simplicity, high efficiency, capability of continuous operation at normal temperature and the like, is widely applied in the field of water treatment, has oxidation resistance and corrosion resistance as well as good chemical stability, and can effectively separate the mixture of the carbonaceous material and water.
Disclosure of Invention
The invention mainly aims to solve the problems that ferrate has limited oxidizing ability and cannot oxidize organic pollutants with low electron cloud density in the water treatment process, and carbon materials can enhance the oxidizing ability of high iron but are difficult to separate and remove from water. The invention provides an activated carbon-ceramic membrane-high active iron catalytic oxidation water treatment method, which utilizes the activated carbon to strengthen the high iron oxidation capacity, utilizes the ceramic membrane to realize the effective separation of the activated carbon and water, and simultaneously effectively relieves the membrane pollution.
An activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method is realized by the following steps.
Firstly, designing and assembling a reactor as shown in figure 1, fixing a ceramic membrane component below the reactor, connecting the ceramic membrane component with a water pump to pump water, arranging an aeration device below the ceramic membrane, and reserving two orifices at the lower side for respectively adding active carbon and ferrate.
Adjusting the pH value of a water sample to be treated to be stable at 6-10, continuously introducing the water sample into the reactor, and simultaneously adding an activated carbon material into the reactor to ensure that the concentration of the activated carbon material in the water sample is 10-100 mg/L.
And thirdly, aerating the reactor, adding ferrate into the water sample at the same time, keeping the concentration of the ferrate at 0.5-5mg/L, and pumping out water after the ferrate, the activated carbon and the water sample to be treated are fully mixed.
The ceramic film is a flat ceramic film.
The activated carbon material is powdered activated carbon or granular activated carbon material, and the concentration is 10-100 mg/L.
The active carbon material is one or more of coal active carbon, wood active carbon or fruit shell active carbon which are mixed according to any proportion.
The water sample to be treated is sewage, surface water, underground water or secondary effluent of a sewage plant containing organic pollutants.
The ferrate is potassium ferrate or sodium ferrate or a mixture of the potassium ferrate and the sodium ferrate, and is added in a solution form, wherein the concentration of the ferrate is 0.5-5 mg/L.
The concentration of ferrate in the ferrate-added water solution is 10mmol/L, and the pH value is 9.
The pH value of the reaction is 6-10.
The basic principle of the water treatment method by catalytic oxidation of activated carbon-ceramic membrane-high-activity iron is as follows: adding a certain amount of Fe (VI) and activated carbon into a water sample to be treated, wherein reducing groups on the surface of the activated carbon can react with ferric iron to generate high-activity pentavalent iron (Fe (V)), quadrivalent iron (Fe (IV)), and the oxidation capacities of the pentavalent iron (Fe (V)) and the quadrivalent iron (Fe (IV)) are far higher than that of the ferrate, so that pollutants which are not easily oxidized by the ferrate can be quickly oxidized, meanwhile, the reducing functional groups on the surface of the activated carbon can activate hydrogen peroxide and oxygen generated in situ to generate hydroxyl radicals or superoxide radicals, and the radicals can also degrade organic pollutants; then, the separation of the activated carbon and the effluent is realized by utilizing the efficient separation function of the ceramic membrane, the effluent quality is ensured, and meanwhile, the membrane pollution problem can be relieved by the oxidation of high-activity iron and free radicals.
The invention relates to a water treatment method by catalytic oxidation of activated carbon-ceramic membrane-high activity iron, which has the following advantages.
(1) The materials adopted by the invention are a flat ceramic membrane, ferrate and an activated carbon material, the ferrate is an environment-friendly oxidant, the activated carbon material is a common water treatment agent, and other toxic and harmful substances are not introduced into the water body, so that the water outlet is safe and reliable.
(2) The invention can rapidly and effectively separate the active carbon from the effluent by utilizing the ceramic membrane, and the oxidation process and the separation process are carried out in the same reactor, thereby greatly shortening the hydraulic retention time, effectively reducing the occupied area of the equipment, and effectively relieving membrane pollution by the oxidation effect and the air aeration stirring effect.
(3) The method is carried out at normal temperature and normal pressure, and has the advantages of simple operation, wide application range, no need of adding additional water treatment equipment, no change of the original treatment process of a water plant, low investment and operation cost and the like.
Drawings
FIG. 1 is a diagram of an apparatus for degrading refractory organic pollutants by using an activated carbon-ceramic membrane-high activity iron catalytic oxidation method for emerging micro-pollutants. FIG. 2 shows the removal efficiency of sulfamethoxazole in example 1, wherein curve 1 is the removal rate curve of activated carbon to pollutants in the example, curve 2 is the removal rate curve of high-iron alone to pollutants in the example, and curve 3 is the removal rate curve of pollutants by using the method of the present invention.
Detailed Description
Embodiments of the present invention are not limited to the specific embodiments listed below, but include any combination between the embodiments.
The first embodiment.
Firstly, designing and assembling a reactor as shown in figure 1, fixing a flat ceramic membrane component below the reactor, connecting the membrane component with a water pump to pump water, arranging an aeration device below the ceramic membrane, and reserving two orifices at the lower side for respectively adding active carbon and ferrate.
Continuously introducing a surface water sample containing sulfamethoxazole into the reactor, adjusting the pH value of the water sample to be treated to enable the pH value to be stable at 8, and simultaneously adding a wood powder activated carbon material into the reactor to enable the concentration of the wood powder activated carbon material in the water sample to be 50 mg/L.
Aerating the reactor, adding potassium ferrate into the water sample at the same time, keeping the concentration of the potassium ferrate at 2.8 mg/L (calculated by Fe), and pumping out water after the ferrate, the activated carbon and the water sample to be treated are fully mixed.
The second specific embodiment: the first difference between this embodiment and the specific embodiment is that: step two, the active carbon material is a granular active carbon material; other steps and parameters are the same as in embodiment one.
The third concrete implementation scheme is as follows: the second embodiment is different from the first embodiment in that: the active carbon material is one or more of coal active carbon, wood active carbon or shell active carbon which are mixed according to any proportion; other steps and parameters are the same as in the second embodiment.
The fourth specific embodiment: this embodiment differs from the first to third embodiments in that: the water sample to be treated is underground water, sewage or secondary effluent of a sewage plant; other steps and parameters are the same as in the first to third embodiments.
The fifth concrete embodiment: the first to fourth differences of this embodiment from the specific embodiments are: step three, the ferrate is sodium ferrate or a mixture of potassium ferrate and sodium ferrate; other steps and parameters are the same as in embodiments one to four.
The sixth specific embodiment: the fifth embodiment is different from the specific embodiment in that: the concentration of ferrate in the ferrate-added water solution is 10mmol/L, and the pH value is 9; the other steps and parameters are the same as those of the fifth and sixth embodiments.
The seventh specific embodiment: the first difference between this embodiment and the specific embodiment is that: the concentration of the active carbon in the second step is any one of 10-100 mg/L.
The specific embodiment eight: the first difference between this embodiment and the specific embodiment is that: the concentration of ferrate in step three is any one of the concentration of 0.5-5 mg/L.
The specific embodiment is nine: the first difference between this embodiment and the specific embodiment is that: and in the second step, the concentration of the organic pollutants is one or a mixture of more of phenol, ciprofloxacin, chloramphenicol, atrazine, bisphenol A, bromophenol, sulfadiazine, propranolol, tetracycline, ofloxacin, tetrabromobisphenol A, carbamazepine and other organic matters.
Claims (7)
1. A method for catalyzing and oxidizing emerging micro pollutants by activated carbon-ceramic membrane-high-activity iron is characterized by comprising the following steps: the method comprises the following steps:
firstly, designing and assembling a reactor as shown in figure 1, fixing a ceramic membrane component below the reactor, connecting the ceramic membrane component with a water pump to pump water, arranging an aeration device below the ceramic membrane, and reserving two orifices at the lower side for respectively adding active carbon and ferrate;
adjusting the pH value of a water sample to be treated to be stable at 6-10, continuously introducing the water sample into the reactor, and simultaneously adding an activated carbon material into the reactor to ensure that the concentration of the activated carbon material in the water sample is 10-100 mg/L;
and thirdly, aerating the reactor, adding ferrate into the water sample to keep the concentration of the ferrate at 0.5-5mg/L, and pumping out water after the ferrate, the activated carbon and the water sample to be treated are fully mixed.
2. The activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method according to claim 1, characterized in that: in the first step, the ceramic membrane is a flat ceramic membrane.
3. The activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method according to claim 1, characterized in that: and step two, the activated carbon material is powdered activated carbon or granular activated carbon material.
4. The activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method according to claim 1, characterized in that: the active carbon material is one or more of coal active carbon, wood active carbon or fruit shell active carbon which are mixed according to any proportion.
5. The activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method according to claim 1, characterized in that: the water sample to be treated is sewage, surface water, underground water or secondary effluent of a sewage plant containing organic pollutants.
6. The activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method according to claim 1, characterized in that: and step three, the ferrate is potassium ferrate or sodium ferrate or a mixture of the potassium ferrate and the sodium ferrate.
7. The activated carbon-ceramic membrane-high activity iron catalytic oxidation water treatment method according to claim 1, characterized in that: the ferrate is added in the form of solution, the concentration of the ferrate in the ferrate aqueous solution is 10mmol/L, and the pH value is 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111634991A (en) * | 2020-05-22 | 2020-09-08 | 陕西科技大学 | Application of modified carbon material in activating ferrate to degrade antibiotic pollutants |
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| SU937343A1 (en) * | 1980-11-28 | 1982-06-23 | Ленинградский Ордена Ленина,Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Горный Институт Им.Г.В.Плеханова | Method of purifying waste water from organic substances |
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| CN108101266A (en) * | 2018-01-31 | 2018-06-01 | 济南大学 | A kind of integrated apparatus and its application method of granular activated carbon coupling ceramic membrane advanced treatment of industrial wastewater |
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| SU937343A1 (en) * | 1980-11-28 | 1982-06-23 | Ленинградский Ордена Ленина,Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Горный Институт Им.Г.В.Плеханова | Method of purifying waste water from organic substances |
| CN105152395A (en) * | 2015-08-25 | 2015-12-16 | 太仓旺泰净化设备有限公司 | Advanced treatment process for paper making waste water |
| CN107651777A (en) * | 2017-10-24 | 2018-02-02 | 哈尔滨工业大学 | A kind of carbonaceous material cooperates with the method for carrying out water process with ferrate |
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Application publication date: 20200214 |